Microbiocidal compositions



United States Patent 3,275,506 MICROBIOCIDAL COMPOSITIONS Karoly Szabo, Yonkers, and Silvio L. Giolito, Whitestone, N.Y., and Thomas B. Williamson, Santa Clara, Calif., assignors to StauflEer Chemical Company, New York, N.Y., a corporation of Delaware No Drawing. Original application June 8, 1961, Ser. No. 116,278. Divided and this application May 14, 1965,

Ser. No. 462,469

Claims." (Cl. 167-42) This application is a division of application Serial No. 116,278, filed June 8, 1961, now abandoned.

This invention relates to halogenated lower alkylalkanethiolsulfonates and, in particular, to chlorinated lower alkylalkan'ethiolsulfonates and to methods of preparing and using such compounds.

The herein described chlorinated lower alkylalkanethiolsulfonates, which are useful as microbiocides, can he formalistically depicted as follows:

wherein R represents a lower alkyl group of from 1 to 2 carbon atoms which may or may not be monochlorinated and R designates a monochlorinated lower alkyl moiety. Compounds falling within the ambit of the above depicted formula which have been found particularly efiicacious as pesticidal agents include those represented by the following sub-generic configuration:

wherein it stands for an integer of from 1 to 4.

Illustrative of structures falling within the definition of formulae I and H are the following:

Compound 1 Compound 2 Compound 3 Compound 4 Compound 5 Compound 6 Compound 7 Compound 8 Compound 9 wherein R and R have the values previously assigned and M represents a metal, preferably an alkali metal such as sodium, potassium and the like. In carrying out the reac- 3,275,506 Patented Sept. 27 1966- tion, it has been our finding that excellent results are obtained when the sodium salt of the lower alkanethiolsulfonate is heated with the necessary brom chlorinated lower alkane in the presence of an organic solvent such as a lower saturated aliphatic alcohol or ketone. After the reaction is completed, the metal salt is removed and the chlorinated alkylalkanethiolsulfonic acid isolated by prooedures commonly employed in the art of organic chemistry, i.e., distillation, crystallization and similar techniques.

The following examples are inserted in order to illustrate, in greater detail, the herein described compounds including their method of preparation and uses thereof.

However, many variations of practicing the invention will occur to those skilled in the art without departing from the spirit or scope of the said invention:

134 g. of methanethiolsulfonic acid sodium salt and 170 g. 1-bromo-2 chloroethane and iso-butanol were placed in a reaction flask equipped With stirrer and reflux condenser and the mixture refluxed (94 C.) for four hours. The sodium bromide Was filtered oil and the solvent removed by distillation under reduced pressure leaving 95 g. of a yellow product having a refractive index of 1.5360 and boiling point of C. at 1.5 mm.

50.0 g. of 3-bromo-1-chloropropane and a 15% mole excess of sodium methanethiolsulfonate in 400 ml. of acetone were refluxed several hours. The sodium bromide was filtered off and the filtrate concentrated in vacuo. The residue of yellow oil amounted to 30 g.

Example 3 CH SO (CH CH Cl Following the procedure as given in Example 1, 1 mole of sodium methanethiolsulfonate was reacted with a 15% mole excess of l-bronro-4-chlorobutane by heating in isobutanol. The product, which is compound 4, was obtained in yields comparable to the first example.

The following example is illustrative of an ethanethiolsulfonate:

Example 4 This compound was formedby condensing 1 mole of sodium ethanethiolsulfonate with a 15 mole excess of l-bromo-2-chloroethane. The reaction was carried out at elevated temperature in iso-butanol. The results and yield paralleled the previous examples.

The chlorinated lower alkylethanethiolsulfonates of this invention are new and valuable compounds which exhibit bactericidal activity against a variety of microorganisms. These compounds are especially potent in controlling certain soil fungi such .as Fusaria, Rhizoctonia, etc. The

:Lowest concentration tested; quantity needed for coni trol may go lower.

=Rhizopus m'gricans. :Stemphyliuru sp,

The new compounds of the present invention are sus- 1 ceptilble to other and numerous modes of application for controlling microorganisms. 1 may be mixed with an inert finely divided solid and ap- For instance, the products plied in the form of dusts or mists. In some instances, it may be desirable to disperse the compounds in water and the so-obtained dispersion employed in the form of a spray. If necessary, surface active agents may be resorted 2 to in order. to facilitate and stabilize the aforesaid dis- 3 persions. In other procedures, the products as herein described can be formulated as oil in water emulsions or water dispersions in which case again, resort may be had to surface active agents to facilitate forming the dispersions. Another application of our compounds includes dissolution in organic solvents followed by spraying the resulting solution in the manner commonly employed in the art.

We claim:

1. The method of inhibiting the growth of bacteria and bactericidal activity of the herein contemplated com- 2 to 4 carbon atoms and R represents lower alkyl of from f pounds are illustrated in Table A: l to 2 carbon atoms.

TABLE A f In vitro vial test Agar plate (bacteria) A Soil bacteria gar Compounds RSSOz-R Fulniga- Asperg. Penicil- Others S. Eruinia Escher. tion, Rhizoctonia Fusarniger lium sp. aureus amylovora Cali Percent Solcmi ium Com ound 9... R1=CH; l P CHT CH2C1 so 100 100 25 25 1 (27 13 Compound 2 R1=CH; 5 50 50 100 10 10 5o 20 v (1a) 7 Com ound 5-.- R =C2H5 P {RAJHPCHZC1 50 25 100 110 110 3 Compound em R=omc1 {Rlvcmo1 5 (5) 10 100 50 500 50 55 1 (27) =Escherichia 001i (bacterium).

Numbers in columns, except those followed by percent, indicate p.p.m. needed for complete control.

Numbers in parentheses indicate partial control at. rate (p.p.m.) shown.

2. The method of inhibiting the growth of bacteria and fungi which comprises applying thereto a small but effective amount of chlorinated lower a1kylalkanethiolsulfo. nate of the following formula:

Y fungi which comprises applying thereto a small but effecfungi which comprises applying there-to a small but efIec- 1 tive amount of chlorinated lower alkylalkanethiolsulfo- 1 nate of the following formula:

wherein R represents monochlorinated lower alkyl of from tive amount of B-chloroethylethanethiolsulfonate..

References Cited by the Examiner UNITED STATES PATENTS 2,877,258 3/1959 Hardy et al 260-453 JULIAN S. LEVIT'IQPrimary Examiner.

STANLEY]. FRIEDMAN, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,275,506 September 27, 1966 Karoly Szabo et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, line 32, the formula should appear as shown below instead of as in the patent:

CH SO S-CH CH -CH Cl Signed and sealed this 12th day of September 1967.

( L) Attest:

ERNEST W. SWIDER Attesting Officer EDWARD J. BRENNER Commissioner of Patents 

1. THE METHOD OF INHIBITING THE GROWTH OF BACTERIA AND FUNGI WHICH COMPRISES APPLYING THERETO A SMALL BUT EFFECTIVE AMOUNT OF CHLORINATED LOWER ALKYLALKANETHIOLSULFONATE OF THE FOLLOWING FORMULA: 